Thermoplastic polyaminoether

ABSTRACT

A novel thermoplastic polyaminoether having good adhesion to asphalt and capable of being prepared at room temperature with short processing time; a multilayer including a layer of a thermoplastic polyaminoether capable of providing a wide operation window; and a thermoplastic asphalt composition including a thermoplastic polyaminoether with a high tensile strength.

FIELD OF THE INVENTION

The present invention relates to a thermoplastic polyaminoether and aprocess for making the same; a multilayer article comprising a layer ofthe thermoplastic polyaminoether and a process for making the same; anda thermoplastic asphalt composition comprising the thermoplasticpolyaminoether and a process for making the same.

INTRODUCTION

Epoxy resins have a wide range of applications thanks to theirsatisfactory bonding and mechanical properties upon curing. For example,thermosetting epoxy resin compositions have been widely used aswaterproofing and bonding layers between bridge decks and upperpavements in road and bridge infrastructure. During curing, oncereaching a tack-free state, these epoxy resin compositions no longerprovide sufficient adhesion to a newly applied substrate. Therefore,upper pavements such as hot mixed asphalt concrete are required to bepaved before epoxy bonding layers reach the tack-free state to avoiddelaminating and/or sliding between them, which limits the operationwindow of these thermosetting epoxy resin compositions.

In contrast, thermoplastic materials such as ethylene vinyl acetate(EVA) plastic membranes for use as waterproofing and bonding layers havelimited processing advantages. For example, when hot mixed asphaltconcrete is applied to the plastic membranes, the plastic membranes meltto bond the asphalt to bridge decks. However, the plastic membranes alsohave some disadvantages including for example, the membranes usuallyprovide unacceptable chemical resistance and adhesion strength to theasphalt and bridge decks.

Another type of thermoplastic waterproofing and bonding layers known inthe art is made from compositions comprising oleylamine and epoxyresins. Due to the slow reaction speed of oleylamine and epoxy resins,drying such compositions is usually too slow (for example, a tack-freetime of greater than 10 hours) to be acceptable in the industry. Addingaccelerators into such compositions can improve the drying speed, butthe use of accelerators usually has the undesirable consequence ofimparting brittleness to the resultant waterproofing and bonding layers.

SUMMARY OF THE INVENTION

The present invention provides a novel thermoplastic material useful forpreparing a waterproofing and bonding layer such as a layer betweenbridge decks and upper pavements in road and bridge infrastructure. Theuse of the novel thermoplastic material of the present inventionshortens the processing time of such material and broadens the operationwindow of such material. In addition, the novel thermoplastic materialhas comparable or even better mechanical properties as compared toconventional thermoplastic resins such as thermoplastic resins made fromoleylamine and epoxy resins; or as compared to conventionalthermosetting epoxy systems.

The present invention includes: (1) a novel thermoplastic polyaminoetherthat can be prepared with a short processing time, as evidenced by afast drying speed (for example, a tack-free time of less than about 7hours) at room temperature (for example, 21-25° C.), and that hascomparable or even better pull-off adhesion strength from asphaltrelative to conventional thermoplastic resins such as thermoplasticresins made from oleylamine and epoxy resins; and a process for makingthe novel thermoplastic polyaminoether; (2) a multilayer article thatcan be used in a wider operation window and that maintains its shearstrength relative to conventional thermosetting epoxy systems; and aprocess for making the multilayer article; and (3) a thermoplasticasphalt composition that has higher tensile strength than conventionalthermoplastic resins such as thermoplastic resins made from oleylamineand epoxy resins.

In a first aspect, the present invention provides a novel thermoplasticpolyaminoether having the structure of Formula (I):

wherein each R₃ has the following structure:

R₁ and R₂ each can be independently a monovalent group selected from analiphatic, cycloaliphatic, aromatic, or polycyclic structure, ormixtures thereof; R can be a straight-chain alkyl with 15 carbonscontaining 0 to 3 C═C bond(s) selected from the group consisting of—C₁₅H₃₁, —C₁₅H₂₉, —C₁₅H₂₇, and —C₁₅H₂₅; R′ can be hydroxyl or hydrogen;R₄ can be a divalent aromatic moiety; R₅ and R₆ each can beindependently

or hydrogen; and n can be an integer from about 1 to about 400.

In a second aspect, the present invention provides a process ofpreparing the novel thermoplastic polyaminoether of the first aspect.The process of preparing the thermoplastic polyaminoether of the firstaspect includes for example the steps of:

(i) reacting the following components: (a) a monoprimary amine, (b)cashew nutshell liquid, and (c) an aldehyde to form a phenalkaminecompound, wherein the molar ratio of the cashew nutshell liquid:aldehyde: monoprimary amine can be for example about1.0:1.0-4.0:1.0-4.0; and

(ii) admixing the phenalkamine compound prepared in step (i) above witha diglycidyl ether, wherein the molar ratio of reactive hydrogens of thephenalkamine compound to oxirane groups of the diglycidyl ether can befor example from about 1:0.5 to about 1:2.

In a third aspect, the present invention provides a multilayer articlecomprising:

a first layer comprising a thermoplastic polyaminoether, wherein thethermoplastic polyaminoether is a reaction product of a phenalkaminecompound having two reactive hydrogen functionalities and a diglycidylether, and wherein the molar ratio of reactive hydrogens of thephenalkamine compound to oxirane groups of the diglycidyl ether is fromabout 1:0.5 to about 1:2; and a second layer comprising asphalt.

In a fourth aspect, the present invention provides a process ofpreparing the multilayer article of the third aspect. The process ofpreparing the multilayer article of the third aspect includes forexample the steps of:

(1) providing a phenalkamine compound having two reactive hydrogenfunctionalities;

(2) admixing the phenalkamine compound with a diglycidyl ether to form areaction mixture, wherein the molar ratio of reactive hydrogens of thephenalkamine compound to oxirane groups of the diglycidyl ether is fromabout 1:0.5 to about 1:2;

(3) applying the reaction mixture to a substrate to form a first layercomprising a thermoplastic polyaminoether;

(4) separately heating asphalt; and

(5) applying the separately heated asphalt onto the first layer to forma second layer, such that the first layer resides between the substrateand the second layer.

In a fifth aspect, the present invention provides a thermoplasticasphalt composition comprising: asphalt; and a thermoplasticpolyaminoether, wherein the thermoplastic polyaminoether is a reactionproduct of a phenalkamine compound having two reactive hydrogenfunctionalities and a diglycidyl ether, and wherein the molar ratio ofreactive hydrogens of the phenalkamine compound to oxirane groups of thediglycidyl ether is from about 1:0.5 to about 1:2.

In a sixth aspect, the present invention provides a process for ofpreparing a thermoplastic asphalt composition of the fifth aspect. Theprocess of preparing the thermoplastic asphalt composition of the fifthaspect includes for example the step of: admixing asphalt and athermoplastic polyaminoether, wherein the thermoplastic polyaminoetheris a reaction product of a phenalkamine compound having two reactivehydrogen functionalities and a diglycidyl ether, and wherein the molarratio of reactive hydrogens of the phenalkamine compound to oxiranegroups of the diglycidyl ether is from about 1:0.5 to about 1:2.

DETAILED DESCRIPTION OF THE INVENTION

The novel thermoplastic polyaminoether of the present invention has thestructure of Formula (I) (hereinafter referred to as “firstthermoplastic polyaminoether”):

wherein R₃ has the following structure:

R₁ and R₂ each can be independently a monovalent group selected from analiphatic, cycloaliphatic, aromatic or polycyclic structure, or mixturesthereof; R can be a straight-chain alkyl with 15 carbons containing 0 to3 C═C bond(s) selected from the group consisting of —C₁₅H₃₁, —C₁₅H₂₉,—C₁₅H₂₇, and —C₁₅H₂₅; and R′ can be hydroxyl or hydrogen; R₄ can be adivalent aromatic moiety; R₅ and R₆ each can be independently

or hydrogen; and n can be an integer from about 1 to about 400, fromabout 2 to about 100 or from about 5 to about 10.

R₁ and R₂ in the above chemical structures each can be independently amonovalent group having from about 2 to about 22 carbon atoms. Forexample, R₁ and R₂ each can be independently a C₂-C₂₂ alkylene orsubstituted alkylene wherein the substituent(s) is arylcarbonyl,alkylcarbonyl, alkylamido, hydroxy, alkoxy, halo, cyano, aryloxy, ormixtures thereof; or a C₆-C₂₂ phenylene group; or mixtures thereof. Theterm “C_(x)” refers to a molecular fragment having x number of carbonatoms where x is a numeric value.

R₁ and R₂ each can also be, for example, independently a monovalentgroup selected

from a cycloaliphatic structure such as

an aromatic structure such as

or a polycyclic structure such as

or mixtures thereof.

In some preferred embodiments, R₁ and R₂ each is independently a C₂-C₂₂hydroxyalkyl group. In a preferred embodiment, both R₁ and R₂ arehydroxyethylene.

R₄ in the above chemical structures may have from about 2 to about 50carbon atoms. R₄ can be a divalent moiety selected fromisopropylidenediphenylene, phenylene, biphenylene, butadiene, hexadiene,ethylene, cyclohexane dimethylene, or combinations thereof. In apreferred embodiment, R₄ has the following structure:

wherein m can be an integer from 0 to about 5 or an integer from about 1to about 4.

In some embodiments, the first thermoplastic polyaminoether of thepresent invention has a viscosity at 120° C. of from about 0.1pascal·second (Pa·s) to about 400 Pa·s, from about 1 Pa·s to about 300Pa·s, or from about 10 Pa·s to about 200 Pa·s, according to the testmethod described in the Examples section below.

The first thermoplastic polyaminoether of the present invention can beprepared from a reaction mixture comprising a phenalkamine compound anda diglycidyl ether, wherein the molar ratio of reactive hydrogens of thephenalkamine compound to oxirane groups of the diglycidyl ether is fromabout 1:0.5 to about 1:2. The phenalkamine compound used to prepare thefirst thermoplastic polyaminoether may be obtained by reacting (a) amonoprimary amine, (b) cashew nutshell liquid (“CNSL”), and (c) analdehyde at the molar ratio of CNSL:aldehyde:monoprimary amine of about1.0:1.0-4.0:1.0-4.0.

The phenalkamine compound used to prepare the first thermoplasticpolyaminoether of the present invention may comprise a compound havingthe following structure:

wherein R₁, R₂, R, and R′ are as previously defined with reference toFormula (I).

The monoprimary amine used to prepare the phenalkamine compound refersto an amine compound having only one primary amine group and containingno secondary or tertiary amine group. The monoprimary amine may be anamine having two active hydrogen atoms that comprises a C₂-C₂₂ carbonatoms aliphatic hydrocarbon group or an alkyl phenol group in which thealkyl group has 2 to 22 carbon atoms. The monoprimary amines may bealkyl amines and substituted alkyl amines, alkanol amines, or mixturesthereof. Examples of suitable monoprimary amines includemonoethanolamine (“2-aminoethanol”); oleylamine; aniline and substitutedanilines such as 4-(methylamido)aniline, 4-methoxyaniline,4-tertbutylaniline, 3,4-dimethoxyaniline, and 3,4-dimethylaniline; octylamine; 1-tetradecylamine; 1-butanamine; cyclohexylamine; benzylamine;dodecanamine; lauryl amine; myristyl amine, palmityl amine; stearylamine; behenyl amine; beef tallow amine; butylamine; 1-aminopropan-2-ol;or mixtures thereof. In some embodiments, monoethanolamine (MEA) is usedin the present invention.

The CNSL used to prepare the phenalkamine compound may comprisecardanol. Cardanol herein refers to a mixture of phenols which containone hydroxyl group and differ in the number of C═C bonds in thealiphatic side chain in the meta-position. The structure of cardanol isshown as the following Formula (III):

wherein R is as previously defined with reference to Formula (I). Thecardanol may be a mixture that variously comprises cardanols havingdifferent R groups.

The concentration of cardanol in the CNSL may be, based on the totalweight of the CNSL, about 10 weight percent (wt %) or more, about 50 wt% or more, or even about 90 wt % or more, and at the same time, about 99wt % or less, about 97 wt % or less, or even about 95 wt % or less.

The CNSL used to prepare the phenalkamine compound may also comprisecardol. Cardol has the following Formula (IV):

wherein R is as previously defined with reference to Formula (I).

The concentration of cardol in the CNSL may be, based on the totalweight of the CNSL, about 0.1 wt % or more, about 1 wt % or more, oreven about 5 wt % or more, and at the same time, about 90 wt % or less,about 50 wt % or less, or even about 10 wt % or less.

The CNSL may also comprise anacardic acid, oligomers of cardanol,oligomers of cardol, and mixtures thereof.

The CNSL used to prepare the phenalkamine compound may be produced fromnatural CNSL through a heating process (for example, at the time ofextraction from cashew nuts), a decarboxylation process, and/or adistillation process. Examples of suitable commercially available CNSLinclude technical cashew nutshell liquid available from Huada Saigao(Yantai) Science & Technology Company Limited.

The aldehyde used to prepare the phenalkamine compound can beformaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde,n-valeraldehyde, caproadlehyde, heptaldehyde, phenylacetaldehyde,benzaldehyde, o-tolualdehyde, tolualdehyde, p-tolualdehyde, furfural,salicylaldehyde (o-hydro-xybenzaldehyde), p-hydroxybenzaldehyde,anisaldehyde, formalin solution, paraformaldehyde, formaldehyde, anysubstituted aldehyde, or mixtures thereof. In a preferred embodiment,formaldehyde or paraformaldehyde is used in the present invention.

The phenalkamine compound used to prepare the first thermoplasticpolyaminoether of the present invention can be prepared according toMannich reaction conditions known in the art. The phenalkamine compoundmay be prepared by providing the aldehyde, the monoprimary amine and theCNSL described above, and reacting them via the Mannich reaction to formthe phenalkamine compound. Solvents such as benzene, toluene or xylenecan be used for removal of water produced during this reaction at anazeotropic distillation point. Nitrogen is also recommended for use toease the water removal. The reaction may be conducted at a temperaturefrom about 60° C. to about 130° C., or from about 80° C. to about 110°C. The initial molar ratio of CNSL:aldehyde:monoprimary amine forpreparing the phenalkamine compound can vary in the range of about1.0:1.0-4.0:1.0-4.0, in the range of about 1.0:1.0-3.0:1.0-3.0, or inthe range of about 1.0:2.0-2.5:2.0-2.5. In some embodiments, the CNSLand the monoprimary amine are mixed, and then the aldehyde is added intothe resulting mixture. Time duration for adding the aldehyde can vary inthe range of from about 0.5 hour to about 2 hours or in the range offrom about 0.6 hour to about 1 hour. The resultant mixture may bepost-treated by distillation under reduced pressure to remove residuevolatiles.

In preparing the first thermoplastic polyaminoether of the presentinvention, the phenalkamine compound described above is further mixedwith one or more diglycidyl ethers, wherein the molar ratio of reactivehydrogens of the phenalkamine compound to oxirane groups of thediglycidyl ether is from about 1:0.5 to about 1:2, from about 1:0.9 toabout 1:1.1, or from about 1:0.95 to about 1:1.05, and preferably about1:1.

The diglycidyl ether useful in the present invention can be solid orliquid. The diglycidyl ether may be based on reaction products ofepichlorohydrin with polyfunctional alcohols, phenols, cycloaliphaticcarboxylic acids, aromatic amines, aminophenols, or mixtures thereof.Examples of suitable diglycidyl ethers include bisphenol A diglycidylether, bisphenol F diglycidyl ether, resorcinol diglycidyl ether,butane-1,4-diol diglycidyl ether, hexane-1,6-diol diglycidyl ether,ethylene glycol diglycidyl ether, cyclohexanedimethanol diglycidylether, or mixtures thereof. In a preferred embodiment, bisphenol Adiglycidyl ether is used in the present invention. Suitable commerciallyavailable diglycidyl ethers may include, for example, D.E.R.™ 331 andD.E.R. 383 epoxy resins both available from The Dow Chemical Company(D.E.R. is a trademark of The Dow Chemical Company).

In preparing the first thermoplastic polyaminoether of the presentinvention, the reaction of the reaction mixture comprising thephenalkamine compound and the diglycidyl ether may be conducted underconditions sufficient to cause the amine moieties to react with epoxymoieties to form a polymer backbone having amine linkages, etherlinkages, and pendant hydroxyl moieties. For example, the temperature ofthe reaction may range from about −20° C. to about 120° C., from about5° C. to about 50° C., or from about 20° C. to about 30° C. The time forthe reaction may be from about 30 seconds to about 28 days or from about1 minute to about 7 days. In some embodiments, the reaction mixturecomprising the phenalkamine compound and the diglycidyl ether showsshorter tack-free time than formulations wherein the phenalkaminecompound is replaced by oleylamine. For example, the tack-free time ofthe reaction mixture may be about 7 hours or less, about 5 hours orless, about 4 hours or less, or even about 3 hours or less, according tothe test method described in the Examples section. Thus, the firstthermoplastic polyaminoether of the present invention can be preparedwith a shorter processing time compared to conventional thermoplasticresins made from oleylamine and epoxy resins which have a tack-free timeof 10 hours or longer. Therefore, the use of the first thermoplasticpolyaminoether of the present invention for paving roads allows for apaved road to open to traffic within a short period of time such as lessthan about 7 hours. The reaction may be conducted in the absence of orin the presence of one or more catalysts to speed up the reaction.Examples of suitable catalysts for the reaction includetris(dimethylaminomethyl)-phenol, bis(dimethylaminomethyl)-phenol,salicylic acid and bisphenol A. When present in the reaction mixture,the amount of the catalyst used may be from 0.1 wt % to 20 wt % or from1 wt % to 5 wt %, based on the weight of the reaction mixture.

The primary two starting materials, described above to produce the firstthermoplastic polyaminoether of the present invention, can be suppliedas two separate components for use in conventional equipment commonlyused for processing a two-component system (the two components referredto herein as “Part A” and “Part B”). During application, Part Acomprising the phenalkamine compound and Part B comprising thediglycidyl ether may be stored in two different tanks. Then when readyfor use, Part A and Part B can be mixed on-site to form the reactionmixture. Then the reaction mixture can be applied to a substrate such asa steel plate, cement concrete, or asphalt concrete.

In another embodiment, the first thermoplastic polyaminoether may besupplied in one-pack system for example wherein the thermoplasticpolyaminoether is in the form of (1) solid flakes or (2) a solution in asolvent.

The present invention also relates to a multilayer article whichincludes a combination of at least two or more layers. In one embodimentfor example, the multilayer article of the present invention maycomprises a first and second layer. The first layer may comprise athermoplastic polyaminoether, and the second layer may comprise anasphalt layer. In one embodiment, the thermoplastic polyaminoether firstlayer of the multilayer article can be any thermoplastic polyaminoetherwhich includes a reaction product of a phenalkamine compound having tworeactive hydrogen functionalities and a diglycidyl ether, wherein themolar ratio of reactive hydrogens of the phenalkamine compound tooxirane groups of the diglycidyl ether may be from about 1:0.5 to about1:2.

For example, in some embodiments, the thermoplastic polyaminoether usedto make the first layer in the multilayer article can be one or morefirst thermoplastic polyaminoethers of Formula (I) described above. Inthese embodiments, the phenalkamine compound having two reactivehydrogen functionalities is a Mannich reaction product of (a) themonoprimary amine described above, (b) the CNSL described above, and (c)the aldehyde described above, wherein the molar ratio of CNSL: aldehyde:monoprimary amine may be in the range of about 1.0:1.0-4.0:1.0-4.0, inthe range of about 1.0:1.0-3.0: 1.0-3.0, or in the range of about1.0:2.0-2.5:2.0-2.5.

In some other embodiments, the thermoplastic polyaminoether used to makethe first layer in the multilayer article can also be, for example, oneor more second thermoplastic polyaminoethers prepared from a polyaminehaving only one primary amine group and only one secondary amine group.In these embodiments, the phenalkamine compound having two reactivehydrogen functionalities is a Mannich reaction product of (a) thepolyamine, (b) the CNSL described above, and (c) the aldehyde describedabove, wherein the molar ratio of CNSL:aldehyde:polyamine may be in therange of about 1.0:0.8-1.8:0.8-1.8, or in the range of about1.0:1-1.5:1-1.5. Examples of suitable polyamines includeN-aminoethylpiperazine (AEP), 1H-imidazole-2-carboxamide,N-methylethylenediamine, N-methyl-1,3-propanediamine, N-coco propylenediamine, or mixtures thereof. In a preferred embodiment, AEP is used asthe polyamine component in the present invention. In some otherembodiments, a mixture of the first and second thermoplasticpolyaminoethers may also be used as the thermoplastic polyaminoether tomake the first layer in the multilayer article.

The first layer of the multilayer article of the present invention mayalso comprise one or more diluents. Examples of suitable diluentsinclude the CNSL described above; nonyl phenol; benzyl alcohol; furfurylalcohol; monoglycidyl compounds such as monoglycidyl ethers, allylmonoglycidyl ethers, phenol monoglycidyl ethers, monoglycidyl esters,C₁₂-C₁₄ alkyl monoglycidyl ethers, or mixtures thereof; diglycidylcompounds such as polyethylene glycol diglycidyl ethers, polypropylenediglycidyl ethers, ethylene oxide-propylene oxide copolymer diglycidylethers, neopentyl glycol diglycidyl ethers, 1,4-butanediol diglycidylether, 1,6-hexanediol diglycidyl ether, cyclohexanedimethanol diglycidylether, bisphenol-A alkoxylate diglycidyl ethers, or mixtures thereof;bisphenol-A alkoxylates; or mixtures thereof. In a preferred embodiment,the first layer useful in the present invention comprises the CNSL. Thediluent may be present, based on the weight of the first layer, in anamount of 0 wt % or more, or even about 1 wt % or more, and at the sametime, about 40 wt % or less, about 30 wt % or less, about 20 wt % orless, or even about 10 wt % or less. The first layer of the multilayerarticle of the present invention may further comprise one or morecatalysts. Catalysts may be any catalysts that can speed up the reactionbetween the diglycidyl ether and the phenalkamine compound having tworeactive hydrogen functionalities. Examples of suitable catalystsinclude tris(dimethylaminomethyl)-phenol,bis(dimethylaminomethyl)-phenol, salicylic acid and bisphenol A, ormixtures thereof. When present, the concentration of the catalyst maybe, based on the weight of the first layer, from about 0.01 wt % toabout 20 wt %, from about 0.1 wt % to about 10 wt %, or from about 1 wt% to about 5 wt %.

The first layer of the multilayer article of the present invention mayfurther comprise aggregates. Aggregates are usually used for manyapplications such as micro-surfacing or slurry seal. Aggregates hereinrefer to a broad category of coarse particulate material used inconstruction, including for example sand, gravel, crushed stone, slag,recycled concrete, geosynthetic aggregates, or mixtures thereof.Aggregates may be selected from dense-graded aggregates, gap-gradedaggregates, open-graded aggregates, reclaimed asphalt pavement, orcombinations thereof. The aggregates may be present in an amount of fromabout 0 wt % to about 99 wt %, from about 10 wt % to about 80 wt %, orfrom about 20 wt % to about 50 wt %, based on the weight of the firstlayer.

The first layer of the multilayer article of the present invention mayfurther comprise fillers. Fillers can be selected from titanium dioxide,barytes, talc, calcytes, clay, kaolin, carbon black, crystalline quartz,magnetite, silicates, aluminum silicates, calcium sulfates, calciumcarbonate, barium salts, or mixtures thereof. The fillers may be presentin an amount of from 0 wt % to about 80 wt %, from about 10 wt % toabout 70 wt %, or from about 20 wt % to about 60 wt %, based on theweight of the first layer.

The first layer of the multilayer article of the present invention mayalso comprise one or more of the following additives: pigments, levelingassistants, flow modifiers, thixotropic agents, adhesion promoters,stabilizers, plasticizers, catalyst de-activators, styrene copolymerssuch as styrene-butadiene rubber (SBR) or styrene-butadiene-styrene(SBS) copolymers, flame retardants, anti-rutting agents, andanti-stripping agents. These additives may be present in a combinedamount of from 0 wt % to about 10 wt % or from about 1 wt % to about 5wt %, based on the weight of first layer.

Generally, the first layer of the multilayer article of the presentinvention may have any desired thickness depending on the application ofthe article. For example, the thickness of the first layer may be fromabout 0.5 millimeter (mm) to about 15 mm in one embodiment, from about0.8 mm to about 10 mm in another embodiment, and from about 1 mm toabout 5 mm in another embodiment.

The second layer of the multilayer article of the present inventioncomprises asphalt. The asphalt useful in the present invention may beany asphalt known in the art, or mixtures of different types of asphalt.Examples of suitable asphalt include heavy traffic asphalt such as AH-70or AH-90 asphalt, polymer-modified asphalt such as SBS- or SBR-modifiedasphalt, or mixtures thereof. The asphalt useful in the presentinvention may have a needle penetration at 25° C. of from 40decimillimeters (dmm) to about 100 dmm, from about 50 dmm to about 90dmm, or from about 60 dmm to about 90 dmm according to the 70604-2011method described in the JTG E20-2011 standard. Suitable commerciallyavailable asphalt useful in the present invention may include, forexample, Zhonghai 70^(#) asphalt, Zhonghai 90^(#) asphalt, Donghai70^(#) asphalt, and Donghai 90^(#) asphalt all available from Sinopec;AH-70^(#) asphalt and AH-90^(#) asphalt both available from Shell; ormixtures thereof. Generally, the second layer of the multilayer articlemay have any desired thickness depending on the application of thearticle. For example, the thickness of the second layer may be fromabout 20 mm to about 150 mm in one embodiment, from about 30 mm to about100 mm in another embodiment, and from about 40 mm to about 60 mm inanother embodiment.

The process of preparing the multilayer article of the present inventioncomprises: (1) providing the phenalkamine compound having two reactivehydrogen functionalities, (2) admixing the phenalkamine compound havingtwo reactive hydrogen functionalities with the diglycidyl ether to forma reaction mixture, wherein the molar ratio of reactive hydrogens of thephenalkamine compound to oxirane groups of the diglycidyl ether is fromabout 1:0.5 to about 1:2; (3) applying the reaction mixture to at leasta portion of the surface of a substrate to form a first layer on atleast a portion of the substrate comprising a thermoplasticpolyaminoether; (4) separately heating asphalt; and (5) applying theseparately heated asphalt onto at least a portion of the first layer toform a second layer on at least a portion of the first layer, such thatthe first layer resides between the substrate and the second layer.

In step (1) of preparing the multilayer article of the presentinvention, the phenalkamine compound having two reactive hydrogenfunctionalities can be prepared by the Mannich reaction of the CNSL, thealdehyde, and the monoprimary amine or the polyamine described above.Conditions of the Mannich reaction are substantially the same as thepreparation of the phenalkamine compound used to prepare the firstthermoplastic polyaminoether of Formula (I) described above. When themonoprimary amine is used, the molar ratio of CNSL: formaldehyde:monoprimary amine may be in the range of about 1.0:1.0-4.0:1.0-4.0, inthe range of about 1.0:1.0-3.0:1.0-3.0, or in the range of about1.0:2.0-2.5:2.0-2.5. When the polyamine is used, the molar ratio ofCNSL:aldehyde:polyamine may be in the range of about1.0:0.8-1.8:0.8-1.8, in the range of about 1.0:1-1.5:1-1.5, or in therange of about 1.0:1-1.1:1-1.1.

In step (2) of preparing the multilayer article of the presentinvention, the reaction conditions, and preferred molar ratios ofreactive hydrogens of the phenalkamine compound to oxirane groups of thediglycidyl ether are the same as in preparing the first thermoplasticpolyaminoether of Formula (I) described above.

In step (3) of preparing the multilayer article of the presentinvention, the substrate may be steel, cement concrete, or asphaltconcrete.

In step (4) of preparing the multilayer article of the presentinvention, the asphalt can be heated to about 120° C. or higher, or evenabout 140° C. or higher.

In preparing the multilayer article of the present invention, the timegap between applying the reaction mixture comprising the phenalkaminecompound having two reactive hydrogen functionalities and the diglycidylether (step (3)) and applying the asphalt (step (5)) can be as short asabout 12 hours or less, or even as short as about 0.5 hours or less. Thetime gap can also be as long as about 2 days or more, or even as long asabout 5 days or more. Thus, the present invention allows a wideoperation window. Compared to conventional thermosetting epoxyformulations, mechanical properties of the multilayer article of thepresent invention is much less sensitive to the time gap. For example,when the time gap changes from about 2 hours to about 1 day, thepull-off adhesion strength of the resultant multilayer articlesdecreases no more than about 50%, or even no more than about 20%. Themultilayer article of the present invention has a much wider operationwindow compared to conventional thermosetting epoxy formulations.

The present invention also relates to a thermoplastic asphaltcomposition (TAC). The TAC of the present invention comprises at leasttwo components including (i) asphalt, and (ii) a thermoplasticpolyaminoether, wherein the thermoplastic polyaminoether is a reactionproduct of a phenalkamine compound having two reactive hydrogenfunctionalities, and a diglycidyl ether, wherein the molar ratio ofreactive hydrogens of the phenalkamine compound to oxirane groups of thediglycidyl ether is from about 1:0.5 to about 1:2, or from about 1:0.9to about 1:1.1. The thermoplastic polyaminoether component present inthe TAC may be substantially the same as the thermoplasticpolyaminoether described above with reference to the multilayer article.

The asphalt component present in the TAC of the present invention issubstantially the same as the asphalt described above with reference tothe multilayer article. The concentration of the asphalt in thethermoplastic polyaminoether may be, based on the total weight of theTAC, about 1 wt % or higher, about 10 wt % or higher, or even about 20wt % or higher, and at the same time, about 99 wt % or lower, about 97wt % or lower, or even about 95 wt % or lower.

The phenalkamine compound having two reactive hydrogen functionalitiesused to prepare the TAC of the present invention is the same as thatdescribed above with reference to the multilayer article.

The TAC of the present invention may further comprise one or morecatalysts. The catalysts may be used to speed up the reaction betweenthe diglycidyl ether and the phenalkamine compound having two reactivehydrogen functionalities. The catalysts can be substantially the same asthose described above with reference to the first layer of themultilayer article. When present, the concentration of the catalyst mayrange, based on the total weight of the TAC, from about 0.01 wt % toabout 20 wt %, from about 0.1 wt % to about 10 wt %, or from about 1 wt% to about 5 wt %.

The TAC of the present invention may further comprise one or morediluents or solvents. Examples of suitable solvents include an alcoholsuch as ethanol, isopropanol, iso- or a normal-butanol, or mixturesthereof; an aromatic hydrocarbon such as benzene, toluene, xylene, ormixtures thereof; a ketone such as methyl isobutyl ketone, methyl ethylketone, cyclohexanone, or mixtures thereof; an ether such as methyltertiary butyl ether, propylene glycol monomethyl ether,tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxy ethane, ethyleneglycol monobutyl ether, or mixtures thereof; an ester such as ethylacetate, butyl acetate, or mixtures thereof; oil of turpentine; aterpene-hydrocarbon oil such as D-limonene, pinene, or mixtures thereof;a high boiling point paraffin type solvent such as a mineral spirit,SOLVESSO™ 100 solvent available from Exxon-Chemical Corporation Co.,Ltd., or mixtures thereof. The diluents in the TAC may include thosediluents in the multilayer article described above. The combinedconcentration of the diluents and solvents in the TAC may be, based onthe total weight of the TAC, 0 wt % or more, about 1 wt % or more, oreven about 2 wt % or more, and at the same time, about 40 wt % or less,about 30 wt % or less, about 20 wt % or less, or even about 10 wt % orless.

In addition to the components described above, the TAC of the presentinvention may further comprise one or more of the additives describedabove in the first layer of the multilayer article. When present, theseadditives may be present in a combined amount of from about 0.001 wt %to about 10 wt % or from about 0.01 wt % to about 2 wt %, based on thetotal weight of the TAC.

The TAC of the present invention may be prepared by mixing thethermoplastic polyaminoether with the diglycidyl ether to form areaction mixture, separately heating asphalt, and mixing the reactionmixture with the separately heated asphalt. Other optional components inthe TAC may be added into the reaction mixture prior to or after mixingwith the asphalt.

The TAC of the present invention provides higher tensile strength atroom temperature than conventional formulations comprising asphalt,epoxy resins, and oleylamine. The TAC of the present invention may beused as water-proofing and/or bonding materials in various applications.In particular, the TAC is suitable for use in road paving andmaintenance applications such as tack coats, fog seals, slurry seals,and micro-surfacing.

EXAMPLES

Some embodiments of the present invention will now be described in thefollowing Examples, wherein all parts and percentages are by weightunless otherwise specified.

D.E.R. 383 resin, available from The Dow Chemical Company, is adiglycidyl ether of bisphenol A and has an epoxy equivalent weight(“EEW”) of from 176 to 183.

D.E.R. 331 resin, available from The Dow Chemical Company, is adiglycidyl ether of bisphenol A and has an EEW of from 182 to 192.

Technical cashew nutshell liquid (“CNSL”), available from Huada Saigao(Yantai) Technology Company Ltd., comprises about 66 wt % of cardanol,about 14 wt % of cardol, and about 20 wt % of polymerized materials,based on the total weight of the technical CNSL.

MARK 135, available from The Dow Chemical Company, includes Part Acomprising a bisphenol A epoxy resin and reactive diluents; and Part Bcomprising an aliphatic amine and diluents.

Oleylamine is used as a curing agent and is available from Rhodia China.

Aminoethylpiperazine (“AEP”) and monoethanoamine (“MEA”) are bothavailable from Sinopharm Chemical Reagent Co., Ltd.

Asphalt 70^(#) is available from Royal Dutch Shell China.

Viscosity Measurement

Viscosity of a thermoplastic resin or a hardener is measured using ARESG2 viscometer of TA Instruments equipped with an environmental chamber.Samples are filled into the gap (from 0 5 mm to 2 mm) between two 25 mmparallel stainless plates and are tested at a shear rate of 100reciprocal second (1/s). The temperature of the environmental chamber isset up at 120° C. when evaluating the thermoplastic resin, or 25° C.when evaluating the hardener, respectively.

Pull-Off Adhesion Test

Ingredients of an epoxy resin composition comprising epoxy resin(s) andan amine compound are mixed and casted on a cement concrete board toform a first layer with a thickness of around 1 mm After one day at roomtemperature, separately heated asphalt (160° C.) is applied to the firstlayer. Then, six dollies are placed onto the surface of the asphalt.After another day at room temperature, a pull-off tester is employed tomeasure the pull-off adhesion strength between the asphalt and the firstlayer by pulling the drawing head at a pulling rate of 150 newtons persecond (N/s) at room temperature.

Shear Strength Test

Ingredients of an epoxy resin composition are mixed and applied to thesurface of a cement concrete with a size of about 40 centimeters (cm) x40 cm. After 2 hours at room temperature, or 1 day at room temperature,respectively, stone mastic asphalt concrete is paved on top of the layerof the epoxy resin composition to form sandwich structured test sampleswith 2-hour time gap, or 1-day time gap, respectively. The layer of theepoxy resin composition serves as a waterproofing and adhesion layerbetween the cement concrete and the asphalt concrete. After another dayof reaction at room temperature, the sandwiched sample is cut into asize of 10 cm×10 cm, and then is tested at a shear rate of 50millimeters per minute (mm/min) with an angle of 30° at roomtemperature. The shear strength of the samples is determined at thefailure point of the samples. The shear strength of the sample with2-hour time gap (the asphalt concrete is applied 2 hours after theapplication of the epoxy resin composition) is denoted as “ShearStrength (2-hour time gap)”. The shear strength of the sample with1-hour time gap (the asphalt concrete is applied 1 day after theapplication of the epoxy composition) is denoted as “Shear Strength(1-day time gap)”.

Drying Time

The drying time of an epoxy resin composition is conducted at roomtemperature according to the ASTM D5895 method “Standard Test Methodsfor Evaluating Drying or Curing During Film Formation of OrganicCoatings Using Mechanical Recorders”. Ingredients of the epoxy resincomposition are mixed and casted on glass panels to form a layer with athickness of 300 μm at room temperature. The drying time is thenmeasured on a Beck Koller drying time recorder.

Tensile Strength

The tensile strength of a thermoplastic asphalt composition is measuredaccording to the ASTM D 638-10 method “Standard Test Method for TensileProperties of Plastics” on an Instron machine at a test speed of 5mm/min and a gauge length of 50 mm The thermoplastic asphalt compositionto be evaluated is casted into a dog bone shape mold and allowed toreact for 7 days at room temperature.

Synthesis of Phenalkamine Compound-I

Phenalkamine Compound-I was prepared as follows. 296.9 grams (g) (1.0mole) of technical CNSL and 122.2 g (2.0 moles) of MEA were mixed in a 1liter round flask equipped with a Dean-Stark water trap connected to arefluxing condenser, a mechanical stirrer and a nitrogen adapter. Themixture was heated to 80° C. With continuous mechanical stirring,nitrogen flow and water circulation, 70.3 g of paraformaldehyde (2.2moles, 94%) was charged into the flask over a time period of 1 hour. Theflask temperature was then raised to 110° C. and 63.7 g of xylene wascharged to initiate a water separation under 0.3 L/min nitrogen flow.When the technical CNSL was consumed, as determined by observing TLCunder 254 nm ultraviolet, the reaction was stopped. The resultantmixture was further treated by distillation under reduced pressure (90°C., 100 mbar vacuums) to remove the residue of xylene and water. Theobtained product had an amine value of 218 milligram potassium hydroxideper gram sample (mg KOH/g) (ISO 9702), a viscosity of 36 Pa·s at 25° C.,and a molecular mass of 464.4 [M+18]⁺ according to LiquidChromatography-Mass Spectrometer (LC-MS) performed on an Agilent 1220.

Synthesis of Phenalkamine Compound-II

Phenalkamine Compound-II was prepared as follows. A 1-litre round flaskwas equipped with a Dean-Stark water trap connected to a refluxingcondenser, a mechanical stirrer and a nitrogen adapter. 296.9 g (1 mole)of technical CNSL and 180.6 g (1.1 moles) of AEP were mixed in the flaskand stirred to be homogeneous; and then the homogeneous mixture washeated to 80° C. With continuous mechanical stirring, mild nitrogen flowand cooling water circulation, 46.3 g (1.15 moles) of paraformaldehydewere charged into the flask. Then, 31.9 g (0.3 mole) of xylene wereadded to the flask and the flask temperature was raised to 110° C. Watergenerated during reaction was removed by xylene under azeotropicdistillation. When the technical CNSL was consumed, as determined byobserving TLC under 254 nm ultraviolet, the reaction was stopped. Theobtained mixture was further treated distillation under reduced pressure(90° C., 100 mbar vacuums) to remove the residue of xylene and water.The resultant product appeared black and viscous; and had a viscosity ofaround 1.082 Pa·s at 25° C., an amine value of 391 mgKOH/g (ISO 9702),and a molecular mass of 444.4 [M+18]⁺ according to LC-MS performed on anAgilent 1220.

Examples (Exs) 1-3 and Comparative Examples (Comp Exs) A-C

Epoxy resin compositions of Exs 1-3 and Comp Exs A-C were prepared bymixing ingredients described in Table 1. Properties of the epoxy resincompositions and the resultant reaction products were evaluatedaccording to the test method described above; and the results of theevaluations are reported in Table 2.

TABLE 1 Epoxy Resin Compositions, weight part Comp Comp Comp ComponentsEx A Ex B Ex C Ex 1 Ex 2 Ex 3 D.E.R. 383 epoxy 52.7 resin D.E.R. 331epoxy 59.4 45.9 46.1 41.4 resin DETA 6.1 MARK 135 Part A 69 MARK 135Part B 31 Phenalkamine 54.1 48.6 Compound-I Phenalkamine 53.9Compound-II Technical CNSL 41.2 10 Oleylamine 40.6

As shown in Table 2, the epoxy resin compositions of Exs 1-2 show a muchshorter drying time (a tack-free time of around 2.6 hours) than theepoxy compositions of Comp Exs A-B (a tack-free time of 10 hours orlonger). The sample of Comp Ex B was still soft one day after mixing theingredients of Comp Ex B. The results in Table 2 indicate that thereactivity of Phenalkamine Compound-I or II with epoxy resins is higherthan that of oleylamine, allowing for a shorter open time (the timeperiod between applying the epoxy composition to a substrate until thesubstrate can be open to traffic).

As shown in Table 2, the reaction products made from the epoxy resincompositions of Exs 1-3 have a viscosity at 120° C. of 137 Pa·s, 48Pa·s, and 130 Pa·s, respectively, which indicates that the reactionproducts of the present invention are thermoplastic.

As shown in Table 2, the pull-off adhesion strength of Exs 1-2 is 2.04megapascals (MPa) and 2.35 MPa, respectively, which are comparable to orbetter than that of the conventional thermoplastic system of Comp Ex B.In contrast, the pull-off adhesion strength of Comp Ex A is only 1.11MPa. The results in Table 2 indicate that the obtained thermoplasticresin of the present invention provides better adhesion to the asphaltcompared to the thermosetting system of Comp Ex A.

TABLE 2 Comp Comp Ex A Ex B Ex 1 Ex 2 Ex 3 Properties of epoxy resincompositions Tack-free time of epoxy resin 10 16 2.6 2.6 — composition,hour Properties of reaction products Viscosity of reaction product — 43137 48 130 at 120° C., Pa · s Pull-off adhesion strength, 1.11 2.00 2.042.35 — MPa

Table 3 shows properties of the reaction products made from the epoxyresin compositions of Ex 3, and Comp Exs A and C. When the time gapbetween the application of the epoxy composition and the asphaltconcrete increased from 2 hours to 1 day, the shear strength of Ex 3only decreased from 6.4 MPa to 5.9 MPa (about 8% decrease) and failureoccurred in either the asphalt concrete or the cement concrete. Theshear strength of Comp Ex A, on the other hand, decreased from 6.7 MPato 2.7 MPa (nearly 60% decrease) and failure occurred on the adhesioninterface. The shear strength of the sample of Comp Ex C was too smallto measure (<0.5 MPa) when the upper asphalt concrete was applied 1 dayafter the application of the epoxy composition of Comp Ex C. The resultsin Table 3 indicate that thermoplastic reaction products of the presentinvention is much less sensitive to the time gap between the applicationof the epoxy resin composition and the upper asphalt concrete,indicating a wider operation window.

TABLE 3 Properties of reaction products Comp Ex A Comp Ex C Ex 3 ShearStrength (2-hour time gap), MPa 6.7 5.2 6.4 Shear Strength (1-day timegap), MPa 2.7 <0.5 5.9 Decrease of shear strength when the time 60% >90%8% gap increased from 2 hours to 1 day

Ex 4 and Comp Ex D

Thermoplastic asphalt compositions of Ex 4 and Comp Ex D were preparedbased on formulations described in Table 4. D.E.R. 331 epoxy resin andan amine compound (Phenalkamine Compound I or oleylamine) were mixed atroom temperature, then added into asphalt which was already separatelyheated to 160° C. to form thermoplastic asphalt compositions of Ex 4 andComp Ex D, respectively. The tensile strength of the obtainedthermoplastic asphalt composition was then evaluated according to thetest method described above; and the results are reported in Table 4. Asshown in Table 4, the thermoplastic asphalt composition of Ex 4 providesa tensile strength of 2.0 MPa which is much higher than that of Comp ExD (0.11 MPa).

TABLE 4 Ex 4 Comp Ex D Component, weight part D.E.R. 331 epoxy resin45.9 59.4 Phenalkamine Compound-I 54.1 — Oleylamine — 40.6 Asphalt70^(#) 150 150 Properties Tensile strength at room 2.00 0.11temperature, MPa

1. A thermoplastic polyaminoether having the structure of Formula (I):

wherein R₃ has the following structure:

wherein R₁ and R₂ each is independently a monovalent group selected froman aliphatic, cycloaliphatic, aromatic, or polycyclic structure, ormixtures thereof; R is a straight-chain alkyl with 15 carbons containing0 to 3 C═C bond(s) selected from the group consisting of —C₁₅H₃₁,—C₁₅H₂₉, —C₁₅H₂₇, and —C₁₅H₂₅; and R′ is hydroxyl or hydrogen; R₄ is adivalent aromatic moiety; R₅ or R₆ is independently

or hydrogen; and n is an integer from 1 to
 400. 2. The thermoplasticpolyaminoether of claim 1, wherein R₁ and R₂ each is independently ahydroxyalkyl group.
 3. The thermoplastic polyaminoether of claim 1,wherein R₄ has the following structure:

wherein m is an integer from 0 to
 5. 4. A process of preparing thethermoplastic polyaminoether of claim 1, comprising: (i) reacting (a) amonoprimary amine, (b) cashew nutshell liquid, and (c) an aldehyde toform a phenalkamine compound, wherein the molar ratio of cashew nutshellliquid: aldehyde: monoprimary amine is 1.0:1.0-4.0:1.0-4.0; and (ii)admixing the phenalkamine compound with a diglycidyl ether, wherein themolar ratio of reactive hydrogens of the phenalkamine compound tooxirane groups of the diglycidyl ether is from 1:0.5 to 1:2.
 5. Theprocess of claim 4, wherein the molar ratio of cashew nutshell liquid:aldehyde:monoprimary amine is 1.0:2.0-2.5:2.0-2.5.
 6. The process ofclaim 4, wherein the phenalkamine compound comprises a compound havingthe following structure:

wherein R₁ and R₂ each is independently a monovalent group selected froman aliphatic, cycloaliphatic, aromatic, or polycyclic structure, ormixtures thereof; R is a straight-chain alkyl with 15 carbons containing0 to 3 C═C bond(s) selected from the group consisting of —C₁₅H₃₁,—C₁₅H₂₉, —C₁₅H₂₇, and —C₁₅H₂₅; and R′ is hydroxyl or hydrogen.
 7. Theprocess of claim 4, wherein the monoprimary amine is monethanolamine 8.A multilayer article comprising: a first layer comprising athermoplastic polyaminoether, wherein the thermoplastic polyaminoetheris a reaction product of a phenalkamine compound having two reactivehydrogen functionalities and a diglycidyl ether, wherein the molar ratioof reactive hydrogens of the phenalkamine compound to oxirane groups ofthe diglycidyl ether is from 1:0.5 to 1:2; and a second layer comprisingasphalt.
 9. The multilayer article of claim 8, wherein the phenalkaminecompound is a Mannich reaction product of (a) a monoprimary amine, (b)cashew nutshell liquid, and (c) an aldehyde, wherein the molar ratio ofcashew nutshell liquid: aldehyde: monoprimary amine is1.0:1.0-4.0:1.0-4.0.
 10. The multilayer article of claim 8, wherein thephenalkamine compound is a Mannich reaction product of (a) a polyaminehaving one primary amine group and one secondary amine group, (b) cashewnutshell liquid, and (c) an aldehyde, wherein the molar ratio of cashewnutshell liquid: aldehyde: polyamine is 1.0:0.8-1.8:0.8-1.8.
 11. Themultilayer article of claim 8, wherein the first layer further comprisesa diluent, a catalyst, fillers, aggregates, or mixtures thereof.
 12. Aprocess of preparing the multilayer article of claim 8, comprising: (1)providing a phenalkamine compound having two reactive hydrogenfunctionalities, (2) admixing the phenalkamine compound with adiglycidyl ether to form a reaction mixture, wherein the molar ratio ofreactive hydrogens of the phenalkamine compound to oxirane groups of thediglycidyl ether is from 1:0.5 to 1:2; (3) applying the reaction mixtureto a substrate to form a first layer comprising a thermoplasticpolyaminoether; (4) separately heating asphalt; and (5) applying theseparately heated asphalt onto the first layer to form a second layer,such that the first layer resides between the substrate and the secondlayer.
 13. The process of claim 12, wherein the phenalkamine compound isprepared by reacting (a) a monoprimary amine or a polyamine having oneprimary amine group and one secondary amine group, (b) cashew nutshellliquid, and (c) an aldehyde, wherein the molar ratio of cashew nutshellliquid: formaldehyde: monoprimary amine is 1.0:1.0-4.0:1.0-4.0, and themolar ratio of cashew nutshell liquid: aldehyde: polyamine is1.0:0.8-1.8:0.8-1.8.
 14. A thermoplastic asphalt composition comprising:asphalt, and a thermoplastic polyaminoether, wherein the thermoplasticpolyaminoether is a reaction product of a phenalkamine compound havingtwo reactive hydrogen functionalities, and a diglycidyl ether, whereinthe molar ratio of reactive hydrogens of the phenalkamine compound tooxirane groups of the diglycidyl ether is from 1:0.5 to 1:2.
 15. Thethermoplastic asphalt composition of claim 14, wherein the phenalkaminecompound is a Mannich reaction product of (a) a monoprimary amine or apolyamine having one primary amine group and one secondary amine group,(b) cashew nutshell liquid, and (c) an aldehyde, wherein the molar ratioof cashew nutshell liquid: aldehyde: monoprimary amine is1.0:1.0-4.0:1.0-4.0, and the molar ratio of cashew nutshell liquid:aldehyde: polyamine is 1.0:0.8-1.8:0.8-1.8.
 16. A process of preparingthe thermoplastic asphalt composition of claim 14, comprising admixingasphalt and a thermoplastic polyaminoether, wherein the thermoplasticpolyaminoether is a reaction product of a phenalkamine compound havingtwo reactive hydrogen functionalities and a diglycidyl ether, andwherein the molar ratio of reactive hydrogens of the phenalkaminecompound to oxirane groups of the diglycidyl ether is from 1:0.5 to 1:2.